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Anilinolysis of Diphenyl Thiophosphinic Chloride and Theoretical Studies on Various R1R2P(O or S)Cl

  • Dey, Nilay Kumar;Han, In-Suk;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.28 no.11
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    • pp.2003-2008
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    • 2007
  • The aminolysis of diphenyl thiophosphinic chloride (2) with substituted anilines in acetonitrile at 55.0 oC is investigated kinetically. Kinetic results yield large Hammett ρX (ρnuc = ?3.97) and Bronsted βX (βnuc = 1.40) values. A concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state is proposed on the basis of the primary normal kinetic isotope effects (kH/kD = 1.0-1.1) with deuterated aniline (XC6H4ND2) nucleophiles. The natural bond order charges on P and the degrees of distortion of 42 compounds: chlorophosphates [(R1O)(R2O)P(=O)Cl], chlorothiophosphates [(R1O)(R2O)P(=S)Cl], phosphonochloridates [(R1O)R2P(=O)Cl], phosphonochlorothioates [(R1O)R2P(=S)Cl], chlorophosphinates [R1R2P(=O)Cl], and chlorothiophosphinates [R1R2P(=S)Cl] are calculated at the B3LYP/ 6-311+G(d,p) level in the gas phase.

Solvent Effect on the Nature of the Metallamacrocycles Formed: Formation of Octanuclear and Dodecanuclear Manganese Metalladiazamacrocycles

  • John, Rohith P.;Lee, Kyung-Jin;Lee, Kyung-Jae;Park, Mi-Ra;Lah, Myoung-Soo
    • Bulletin of the Korean Chemical Society
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    • v.28 no.11
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    • pp.2009-2014
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    • 2007
  • The aminolysis of diphenyl thiophosphinic chloride (2) with substituted anilines in acetonitrile at 55.0 oC is investigated kinetically. Kinetic results yield large Hammett ρX (ρnuc = ?3.97) and Bronsted βX (βnuc = 1.40) values. A concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state is proposed on the basis of the primary normal kinetic isotope effects (kH/kD = 1.0-1.1) with deuterated aniline (XC6H4ND2) nucleophiles. The natural bond order charges on P and the degrees of distortion of 42 compounds: chlorophosphates [(R1O)(R2O)P(=O)Cl], chlorothiophosphates [(R1O)(R2O)P(=S)Cl], phosphonochloridates [(R1O)R2P(=O)Cl], phosphonochlorothioates [(R1O)R2P(=S)Cl], chlorophosphinates [R1R2P(=O)Cl], and chlorothiophosphinates [R1R2P(=S)Cl] are calculated at the B3LYP/ 6-311+G(d,p) level in the gas phase.

Study of MgSrO and MgCaO thin films as protective layers for PDPs

  • Matulevich, Y.T;Moon, Sung-Hwan;Choi, Jong-Seo;Zang, Dong-Sik
    • 한국정보디스플레이학회:학술대회논문집
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    • 2009.10a
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    • pp.181-183
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    • 2009
  • Comparative study of the dependence of the firing voltage of MgSrO and MgCaO protective layers on chemical composition was carried out. It was observed that the firing voltage increases when CaO/MgO or SrO/MgO ratio increases.

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Flux Melting Route to 2-and 3-dimensional Fibrous Potassium Titanates, K$_2Ti_{2n}O_{4n+1}$ (n = 2 and 3) (Flux 용융법에 의한 2차원 및 3 차원 구조의 티탄산칼륨 섬유의 합성)

  • Jin-Ho Choy;Yang Su Han;Seung Wan Song
    • Journal of the Korean Chemical Society
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    • v.37 no.8
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    • pp.765-772
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    • 1993
  • Two-dimensional potassium tetratitanate ($K_2Ti_4O_9$) and three-dimensional potassium hexatitanate ($K_2Ti_6O_{13}$) fibers have been prepared by the combined method consisting of the flux melting (1150$^{\circ}C$)-slow cooling (cooling rate = 5$^{\circ}C$/h) process from the starting raw materials of $K_2CO_3$, and $TiO_2$ with the flux of $K_2MoO_4$. It was found that the fiber growth reaction is strongly dependent upon the mole ratio of flux (F) to raw material (R), which is 7 : 3 (F : R) as for the optimum growth condition. Relatively long fibers (average length ${\thickapprox}$ 4 mm) with a mixture of $K_2Ti_4O_9$ (major) and $K_2Ti_6O_{13}$ (minor) could be obtained when the reaction was carried out for the $K_2MoO_4-$K_2O{\cdot}4TiO_2$ (F : R = 7 : 3) system, but for the $K_2$MoO_4$-$K_2O{\cdot}6TiO_2$ (F : R = 7: 3) one, only the short fibers with ${\thickapprox}$ 2 mm long could be grown as the mixed phase of $K_2Ti_6O_{13}$ and $K_2Ti_4O_9$.

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A Characterization Study on Nafion$^{(R)}$/$ZrO_2-TiO_2$ Composite Membranes for PEMFC Operation at High Temperature and Low Humidity (고온/저가습 PEMFC 운전을 위한 Nafion$^{(R)}$/$ZrO_2-TiO_2$ 복합 전해질 막의 특성 연구)

  • Park, Ki-Tae;Chun, Jeong-Hwan;Choi, Dong-Woong;Kim, Sung-Hyun
    • Transactions of the Korean hydrogen and new energy society
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    • v.22 no.1
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    • pp.60-68
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    • 2011
  • [ $ZrO_2-TiO_2$ ]binary oxides with various Zr:Ti molar ratios were prepared by sol-gel method and Nafion$^{(R)}$/$ZrO_2-TiO_2$ composite membranes were fabricated for proton exchange membrane fuel cells (PEMFCs) at high temperature and low humidity. Water uptake, Ion exchange capacity (IEC), and proton conductivity of Nafion$^{(R)}$/$ZrO_2-TiO_2$ composite membranes were characterized and these composite membranes were tested in a single cell at $120^{\circ}C$ with various relative humidity (R.H.) conditions. The obtained results were compared with the unmodified membranes (Nafion$^{(R)}$ 112 and Recast Nafion$^{(R)}$). A Nafion$^{(R)}$/$ZrO_2-TiO_2$ composite membrane with 1:3 of Zr:Ti molar ratio showed the highest performance. The performance showed 500 mW/$cm^2$ (0.499V) at $120^{\circ}C$, 50% R. H., and 2 atm.

Joining Behavior of YSZ Ceramics to Al2O3-ZrO2-SiO2-R2O and Al2O2-ZrO2-SiO2-La2O3-R2O Glass Systems (Al2O3-ZrO2-SiO2-R2O와 Al2O3-ZrO2-SiO2-La2O3-R2O계 유리와 부분안정화 지르코니아간의 접합거동)

  • Choi, Jinsam;Bae, Won Tae
    • Journal of the Korean Ceramic Society
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    • v.52 no.1
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    • pp.19-22
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    • 2015
  • The joining behavior of YSZ ceramics to the glasses used in the $9Al_2O_3-24ZrO_2-51SiO_2-16R_2O$ and $9Al_2O_3-24ZrO_2-51SiO_2-7La_2O_3-9R_2O$ (wt%) glass systems was investigated. The glass transition and softening temperatures were determined to be $430^{\circ}C$ and $760^{\circ}C$, respectively. The behavior of the contact angle was inversely proportional to an increase in the temperature. The Zr element in YSZ acted as a nucleation agent and contributed to the bonding behavior at the interface.

A Study on the New Development for Determination of Dead Time in GC-OTC/FID (GC-OTC/FID에서 Dead Time 결정을 위한 새로운 방법 개발에 대한 연구)

  • Oh, Doe Seok;Kim, Sung Wha;Ko, Eun Ah;Jeon, Hyung Woo
    • Journal of the Korean Chemical Society
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    • v.63 no.4
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    • pp.246-252
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    • 2019
  • In the system of GC-OTC/FID (Gas chromatography-Open Tubular Column/Flame Ionization Detector), DMSO (Dimethyl sulfide) solvent was used to separate the polar solvents (Alcohols). In this system DMSO was eluted later than the separated polar solvents. At this system to calculate chromatographic factors [adjusted retention time ($t_R^{\prime}=t_R-t_O$), capacity factor{$k^{\prime}=(t_R-t_O)/t_O$} and separation factor {${\alpha}=(t_{R2}-t_O)/(t_{R1}-t_O)$}], dead time($t_O$) is necessary, but the method to calculate it has not been reported yet. Therefore, we have tried to develop $t_O$. To calculate $t_O$, we conversed DMSO retention time (DMSO $t_R$) to logarithm ($f(x)={\log}\;t_{R(DMSO)}{\rightarrow}t_O$, $t_O={\log}$ 9.551=0.980). To confirm the optimization of the developed method, we compared with $CH_4\;t_R$ and ${\ln}\;t_{R(DMSO)}$. Both of the values calculated by $CH_4\;t_R$ and ${\ln}\;t_{R(DMSO)}$ were not suitable in the calculation k' and ${\alpha}$. The developed method in this study{${\log}\;t_{R(DMSO)}$} has satisfied both of the values k' criteria (1${\alpha}(1<{\alpha}<2)$. The developed calculation method in this study was easy and convenient, therefore it can be expected to be applied to these similar systems.

Study on the R-curve Behaviour in $Al_2O_3-ZrO_2-SiC$ Whisker Comosite ($Al_2O_3-ZrO_2-SiC$ Whisker 복합재료에서의 R-curve 거동에 관한 연구)

  • Kim, Hyun-Ha;Park, Hyun;Choi,Sung-Churl
    • Journal of the Korean Ceramic Society
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    • v.30 no.9
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    • pp.731-739
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    • 1993
  • R-curve measurements were performed on Al2O3(matrix)-ZrO2-SiC whisker composite and Al2O3-ZrO2, Al2O3-SiC whisker composites in the favor of comparing the effect of ZrO2 and SiC whisker, as a second phase, to Al2O3 matrix. Al2O3-SiC whisker and Al2O3-ZrO2-SiC whisker were fabricated by hot pressing at 1$700^{\circ}C$, 15MPa and Al2O3-ZrO2 by pressureless sintering at 1$600^{\circ}C$. A controlled flaw/strength technique was utilized to determine fracture resistance as a function of crack extension and R-curve behaviour was determined from the relationship which is KR=K0(Δa)m. R-curveresults were KR=6.173$\times$Δa0.031 for Al2O3-ZrO2, KR=18.796$\times$Δa0.172 for Al2O3-SiC whisker and KR=11.96$\times$Δa0.110 for Al2O3-ZrO2-SiC whisker composite. From the analysis of R-curve and expeirmental data above three composites, it is found that R-curve behaviour of Al2O3-ZrO2-SiC whisker composite was dominated initially by the strengthening effect of ZrO2 and after, some extended crack were influenced by the effect of SiC whisker. Analysis of SEM and X-ray data revealed that whisker bridging in the crack wake and whisker pull-out mechanisms were the main mechanism for the R-curve behaviour.

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